Tetrahydropyran-2-yl-3-methoxyphenyl ether (10 g, 48.1 mmol) was used as starting material and dissolved in 100 mL of tetrahydrofuran. Over 15 min, n-butyllithium (1.6 M hexane solution, 33 mL, 52.8 mmol) was added dropwise to this solution. After the dropwise addition, the reaction mixture was stirred at room temperature for 2.5 hours. Subsequently, the reaction mixture was cooled to 0 °C and 1,2-dibromoethane (4.6 mL, 53.2 mmol) was added dropwise. After completion of the dropwise addition, the reaction mixture was stirred at room temperature for about 14 hours. After the reaction was complete, the reaction mixture was diluted with 50 mL of 1N hydrochloric acid and stirred for 1 hour. The aqueous phase was extracted with three 100 mL portions of diethyl ether. The organic phases were combined and fully extracted with 5N sodium hydroxide solution. Combine the basic aqueous phase extracts and cool in an ice/water bath. The pH of the aqueous solution was adjusted to about 1 with 5N hydrochloric acid and then extracted with three 100 mL portions of diethyl ether. The ether extracts were combined, washed with saturated aqueous sodium chloride, dried over magnesium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography using a gradient elution with hexane containing 0 to 10% ethyl acetate. The grades containing the target product 2-bromo-3-methoxyphenol were combined and concentrated under reduced pressure to give a residue of 2.91 g (30% yield), which was left to crystallize. Elemental Analysis (EA): C7H7BrO2 Calculated values: C, 41.41; H, 3.48. Measured values: C, 41.81; H, 3.46.
